CN104907018B - A kind of three-dimensional metatitanic acid/graphene oxide pluralgel and preparation method thereof - Google Patents

A kind of three-dimensional metatitanic acid/graphene oxide pluralgel and preparation method thereof Download PDF

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CN104907018B
CN104907018B CN201510271307.XA CN201510271307A CN104907018B CN 104907018 B CN104907018 B CN 104907018B CN 201510271307 A CN201510271307 A CN 201510271307A CN 104907018 B CN104907018 B CN 104907018B
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graphene oxide
pluralgel
metatitanic acid
mixed solution
acetic acid
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CN201510271307.XA
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CN104907018A (en
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周国伟
刘蕊蕊
陈兴芬
刘作花
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齐鲁工业大学
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Abstract

The invention discloses a kind of three-dimensional metatitanic acid/graphene oxide pluralgel and preparation method thereof, the pattern of this pluralgel forms fiber cluster by some nanofibers, and fiber cluster is cross-linked and reticulates structure.The present invention adopt simply, a step solvent-thermal method of environmental protection with positive four butyl esters of graphene oxide and metatitanic acid as raw material, acetic acid is synthesized for solvent.By regulating and controlling the mass ratio of graphene oxide and TBT, to control formability and the stability of gel, by changing the consumption of acetic acid, to control the microscopic appearance of gel.Metatitanic acid/current document of graphene oxide pluralgel that the present invention prepares three dimensional structure was not reported, structure is novel, excellent performance.The pattern of metatitanic acid/graphene oxide pluralgel of three dimensional structure of present invention preparation and performance are controlled.The metatitanic acid of prepared three dimensional structure/graphene oxide pluralgel not only has the build-in attribute of metatitanic acid and graphene oxide additionally it is possible to produce novel cooperative effect.

Description

A kind of three-dimensional metatitanic acid/graphene oxide pluralgel and preparation method thereof
Technical field
The present invention relates to graphene oxide gel and its preparing technical field, more particularly, to a kind of morphology controllable have three Metatitanic acid/graphene oxide pluralgel of dimension structure and preparation method thereof.
Background technology
At present, self-assembling technique is considered to build a kind of most efficient method of the nano material of macroscopic three dimensional structure One of.The Graphene of two-dimensional structure or graphene oxide are self-assembled into the nano material of three dimensional structure(As hydrogel, airsetting Glue, other micropores or large pore material)There has been very big progress, and show in the fields such as energy storage, catalysis, environmental conservation Go out much excellent, unique performance.Due to strong π-π effect and Van der Waals force between the stannic oxide/graphene nano piece of two dimension, easily In cause irreversible assemble and pile up, the very big specific surface area reducing graphene oxide, thus limiting graphite oxide Much potentially the applying of alkene material or graphene oxide based composites.At present, the progress of a leap is by self assembly Method is come to prepare the graphene oxide gel of independent three dimensional structure be to solve a kind of effective method of these problems and means.This It is because the nano material of three dimensional structure is three-dimensional porous cross-linked structure, there is larger specific surface area, high electric conductivity, strong Mechanical performance and chemical stability.
Polymer, noble metal or metal-oxide are modified to graphene oxide gel or functionalization not only can be simultaneously Keep the inherent character of graphene oxide and modified material, and the cooperative effect of novelty can be produced.For example, He et al. exists A kind of MnO is reported on ACS Nano 1 (2013) 174 1822The tridimensional network of coated graphite alkene, has independent, clever The characteristic of work, lightweight and high connductivity, has larger specific surface area(392 m2g-1), higher specific capacity(130 F g-1)With Outstanding mechanical performance.Yu et al. is in ACS Nano 4 (2010) 7358??Report graphene oxide and DNA on 7362 It is self-assembly of multi-functional hydrogel, the hydrogel of synthesis has high mechanical strength, environmental stability, dye load energy Power.Publication No. is CN 102350335 A(Application number 201110228107.1)Chinese patent literature disclose a kind of room temperature system The method of standby nanometer titanium dioxide/graphene composite aquogel.It is at room temperature, nano titanium oxide is added to containing reduction In the graphene oxide water solution of agent, ultrasonic disperse obtains presoma;Then above-mentioned precursor solution is stood instead at room temperature After answering 8 16 h, obtain final product product, by obtained products application in light-catalysed research.The weak point of this invention:Tested Poisonous reagent hydration hydrazine, not environmental protection is used in journey;Pattern and performance are uncontrollable;Nano titania in the composite Particle is easy to assemble;In photocatalytic pollutant degradation, composite is not easy to recycling.
Publication No. is CN 102423702 A(Application number 201110456027.8)Chinese patent literature disclose one kind Graphene oxide/titanic oxide composite photochemical catalyst material and preparation method thereof.Graphene oxide is configured to aqueous solution, by poly- second Glycol, glacial acetic acid, butyl titanate are added in ethanol and are made into mixed liquor, add graphene oxide in this mixed solution, Under room temperature, stirring forms mixed liquor, through washing, dry, calcining and other processes acquisition product.The structure of this composite photocatalyst material: A kind of nano level titanium dioxide is dispersed on micron-sized graphene oxide sheet.The shortcoming of this patent:It is dispersed in graphite oxide Titanium dioxide on alkene piece is easy to assemble, and does not have the pattern of fixation;Experimentation is loaded down with trivial details, and the response time is oversize, needs room temperature Stir 15 days;Calcining affects its pattern and performance, requires harshness to the condition of calcining.Metatitanic acid currently for three dimensional structure/ Graphene oxide pluralgel has no report, and the more worth research of controllability of its pattern, performance.
Content of the invention
It is an object of the invention to provide a kind of three-dimensional metatitanic acid/graphene oxide pluralgel and preparation method thereof, this gel Structure is novel, have larger specific surface area, excellent performance, and this preparation method is simple and environmentally-friendly.
For achieving the above object, the technical solution used in the present invention is:
A kind of three-dimensional metatitanic acid/graphene oxide pluralgel, the metatitanic acid/graphene oxide pluralgel of this three dimensional structure Pattern forms fiber cluster by some nanofibers, and fiber cluster is cross-linked and reticulates structure, wherein single nanofiber A diameter of 35 55 nm, length be 5 50 μm.
A kind of preparation method of three-dimensional metatitanic acid/graphene oxide pluralgel, comprises the following steps:
(1)Prepare graphene oxide;
With graphite powder as raw material, jonquilleous acidic oxidation graphene aqueous solution is obtained using modified Hummers method, Through washing centrifugation repeatedly, ultrasonic 0.5 1 h, obtain graphene oxide solution, graphene oxide solution now close in Property, through being dried to obtain the graphene oxide of lamellar, grind and make powder, the method is simple and convenient to be easy to get.Graphene oxide Preparation belongs to ordinary skill in the art means, is not merely defined to the method.
Wherein, the quality of described graphite powder is 2 ~ 3g, and described drying is lyophilization.
(2)Hydrolytic process:By positive for metatitanic acid four butyl esters(TBT)It is added in acetic acid, after stirring, form mixed solution A;
Wherein, the reaction temperature of hydrolytic process is 30 40 °C, TBT and acetic acid(V1)Volume ratio be:(0.1~1):(30~ 50), mixing time is 12 ~ 24h.Note:TBT is slowly added into acetic acid, suppression hydrolysis, prevents from reuniting.
(3)Prepare graphene oxide acetum:
Take step(1)Preparation graphene oxide mix with acetic acid, ultrasonic after obtain graphene oxide acetum;
Wherein, described graphene oxide and acetic acid(V2)Mass volume ratio be:(2~24):(5~40)Mg/mL, preferably than Example be(6~24):(10~40), ultrasonic time is 0 ~ 1h.
(4)Self assembling process:
The mixed solution A that be obtained step (2) and the graphene oxide acetum that obtains of step (3) mix, 30 ~ 40 °C of lower self assembly stirrings form mixed solution B.
Preferably operating procedure is:Under conditions of being stirred continuously, graphene oxide acetum that step (3) is obtained It is added in the mixed solution A that step (2) is obtained, form mixed solution B in 30 ~ 40 °C of lower self assembly stirrings.This process Purpose is to prevent from individually piling up between graphene oxide sheet and piece it is impossible to be combined with titanium source.
Wherein, the time of self assembly stirring is 12 h.
(5)By step(4)The mixed solution B obtaining is incubated 12 ~ 24h at 120 ~ 180 DEG C, after solvent heat treatment, is cooled to Room temperature, that is, obtain metatitanic acid/graphene oxide pluralgel.
Step(5)Specific operating procedure be:It is anti-that the mixed solution B obtaining transfers to teflon-lined high pressure Answer in kettle;Autoclave is tightened and puts in baking oven, be incubated 12 ~ 24h at 120 ~ 180 DEG C;After solvent heat treatment, high pressure is anti- Answer kettle to naturally cool to room temperature, that is, obtain metatitanic acid/graphene oxide pluralgel.
The volume of described teflon-lined autoclave is 100ml.
The present invention passes through to regulate and control the mass volume ratio of graphene oxide and TBT, to control formability and the stability of gel, By changing the consumption of acetic acid, to control the microscopic appearance of gel
Step(2)、(3)In, described TBT with the volume mass ratio of graphene oxide is:(0.1~1):(2~24)mL/mg. Described step(2)Middle acetic acid(V1)With step(3)In acetic acid(V2)Volume ratio be:(30~50):(5~40), preferred ratio For V1:V2=36.75:(10~40).
Step(2)In, described hydrolytic process condition is 40 DEG C of holding 24 h.
Step(2)In, described TBT with the volume ratio of acetic acid is:1:36.75.
Step(4)In, described self assembling process condition is 40 DEG C of holding 2 h.
Step(5)In, described solvent thermal process treatment conditions are 150 DEG C of holding 24 h.
The invention has the beneficial effects as follows:
The pattern of the metatitanic acid/graphene oxide pluralgel of the three dimensional structure being obtained using the method for the present invention is by one The fiber composition fiber cluster of root, two or more than three, fiber cluster reconnects and reticulates the gel of structure, wherein single receives About in 35 55 nm, length reaches tens microns to the diameter of rice fiber.
Metatitanic acid/current document of graphene oxide pluralgel that the present invention prepares three dimensional structure did not report, structure is new Grain husk, excellent performance.
Metatitanic acid/graphene oxide the pluralgel of the three dimensional structure of present invention preparation has larger specific surface area, plays Three dimensional structure is better than the advantage of two-dimensional structure, is that next step application lays the foundation.
Metatitanic acid/graphene oxide the pluralgel of the three dimensional structure of present invention preparation not only has metatitanic acid and graphene oxide Build-in attribute additionally it is possible to produce novel cooperative effect.
The pattern of metatitanic acid/graphene oxide pluralgel of three dimensional structure of present invention preparation and performance are controlled.
The present invention prepares relatively easy, the used raw material of method of the metatitanic acid/graphene oxide pluralgel of three dimensional structure Inexpensive, be easy to get, safety.
Brief description
Fig. 1 is the macrograph of metatitanic acid/graphene oxide pluralgel and the cross section FESEM of the embodiment of the present invention 2 preparation: In Fig. 1, a is the macrograph of embodiment 2;In Fig. 1, b is the cross section FESEM figure of embodiment 2.
Fig. 2 is the HRTEM of the metatitanic acid/graphene oxide pluralgel prepared by different acetic acid and graphene oxide consumption Figure:In Fig. 2, a is the HRTEM of embodiment 1;In Fig. 2, b is the HRTEM of embodiment 2;In Fig. 2, c is the HRTEM of embodiment 3;Figure In 2, d is the HRTEM of embodiment 4;In Fig. 2, e is the HRTEM of embodiment 5;In Fig. 2, f is the HRTEM enlarged drawing of embodiment 5.
Fig. 3 is the FESEM figure of the metatitanic acid/graphene oxide pluralgel prepared by different graphene oxide consumptions:In Fig. 3 A is the FESEM of embodiment 2;In Fig. 3, b is the FESEM of embodiment 3;In Fig. 3, c is the FESEM of embodiment 4;In Fig. 3, d is real Apply the FESEM of example 5.
Fig. 4 is the Raman spectrogram of metatitanic acid/graphene oxide pluralgel:In Fig. 4, a is the Raman spectrogram of embodiment 1; In Fig. 4, b is the Raman spectrogram of embodiment 2;In Fig. 4, c is the Raman spectrogram of embodiment 3;In Fig. 4, d is drawing of embodiment 4 Graceful spectrogram.
Fig. 5 be metatitanic acid/graphene oxide pluralgel and pure metatitanic acid under ultraviolet light to methyl orange(Initial concentration is 30mg/L)Photocatalytic degradation figure, i.e. change over time, the variation diagram of the concentration of methyl orange and initial concentration ratio.Sample Concentration in methyl orange solution for the product is 0.2 g/L.
Specific embodiment
The present invention is further described with reference to the accompanying drawings and examples.
Embodiment 1:
A kind of three-dimensional metatitanic acid/graphene oxide pluralgel, the metatitanic acid/graphene oxide pluralgel of this three dimensional structure Pattern forms fiber cluster by the nanofiber of, two or more than three, and fiber cluster is cross-linked and reticulates structure Gel, the diameter of wherein single nanofiber is about 35 55 nm, and length reaches tens microns.As shown in Fig. 2 a in Fig. 2 HRTEM figure for the present embodiment pluralgel.In Fig. 4, a is the Raman spectrogram of the present embodiment.
The preparation method of described three-dimensional metatitanic acid/graphene oxide pluralgel is as follows:
(1)With 3 g graphite powders as raw material, jonquilleous acidic oxidation Graphene water is obtained using modified Hummers method Solution, through washing centrifugation repeatedly, ultrasonic 0.5 h, obtains the graphene oxide solution close to neutrality, obtains through lyophilization To the graphene oxide of lamellar, grind and make powder;
(2)Hydrolytic process:Under 40 °C, 1 ml TBT is slowly added in 36.75 ml acetic acid, shape after stirring 24 h Become mixed solution A;
(3)Take 6 mg graphene oxides prepared by step (1) to be added in 5 ml acetic acid, after ultrasonic 0.5 h, obtain oxidation Graphene acetum;
(4)Self assembling process:Under conditions of being stirred continuously, the graphene oxide acetum that step (3) is obtained adds Enter in the mixed solution A being obtained to step (2), stir 2 H-shapeds in 40 °C of lower self assemblies and become mixed solution B;
(5)By step(4)The mixed solution B obtaining transfers to the teflon-lined autoclave of 100 mL In;
(6)Solvent thermal process:Autoclave in step (5) is tightened and puts in baking oven, be incubated 24 h at 150 DEG C; After solvent heat treatment, autoclave is naturally cooled to room temperature, that is, obtain metatitanic acid/graphene oxide pluralgel.
Embodiment 2:
A kind of three-dimensional metatitanic acid/graphene oxide pluralgel, the metatitanic acid/graphene oxide pluralgel of this three dimensional structure Pattern forms fiber cluster by the nanofiber of, two or more than three, and fiber cluster is cross-linked and reticulates structure Gel, the diameter of wherein single nanofiber is about 35 55 nm, and length is about 5 50 μm.As shown in figure 1, in Fig. 1 A is the macrograph of the present embodiment pluralgel;In Fig. 1, b is the cross section FESEM figure of the present embodiment pluralgel.As Fig. 2 institute Show, in Fig. 2, b is the HRTEM figure of the present embodiment pluralgel.In Fig. 3, a is the FESEM figure of the present embodiment pluralgel.B in Fig. 4 Raman spectrogram for the present embodiment.
The preparation method of described three-dimensional metatitanic acid/graphene oxide pluralgel is as follows:
(1)With 3 g graphite powders as raw material, jonquilleous acidic oxidation Graphene water is obtained using modified Hummers method Solution, through washing centrifugation repeatedly, ultrasonic 0.5 h, obtains the graphene oxide solution close to neutrality, obtains through lyophilization To the graphene oxide of lamellar, grind and make powder;
(2)Hydrolytic process:Under 40 °C, 1 ml TBT is slowly added in 36.75 ml acetic acid, shape after stirring 24 h Become mixed solution A;
(3)Take 6 mg graphene oxides prepared by step (1) to be added in 20 ml acetic acid, after ultrasonic 0.5 h, obtain oxidation Graphene acetum;
(4)Self assembling process:Under conditions of being stirred continuously, the graphene oxide acetum that step (3) is obtained adds Enter in the mixed solution A being obtained to step (2), stir 2 H-shapeds in 40 °C of lower self assemblies and become mixed solution B;
(5)By step(4)The mixed solution B obtaining transfers to the teflon-lined autoclave of 100 mL In;
(6)Solvent thermal process:Autoclave in step (5) is tightened and puts in baking oven, be incubated 24 h at 150 DEG C; After solvent heat treatment, autoclave is naturally cooled to room temperature, that is, obtain metatitanic acid/graphene oxide pluralgel.
Embodiment 3:
A kind of three-dimensional metatitanic acid/graphene oxide pluralgel, the metatitanic acid/graphene oxide pluralgel of this three dimensional structure Pattern forms fiber cluster by the nanofiber of, two or more than three, and fiber cluster is cross-linked and reticulates structure Gel, the diameter of wherein single nanofiber is about 35 55 nm, and length is about 5 50 μm.As shown in Fig. 2 in Fig. 2 C is the HRTEM figure of the present embodiment pluralgel.In Fig. 3, b is the FESEM figure of the present embodiment pluralgel.In Fig. 4, c is this enforcement The Raman spectrogram of example.
The preparation method of described three-dimensional metatitanic acid/graphene oxide pluralgel is as follows:
(1)With 3 g graphite powders as raw material, jonquilleous acidic oxidation Graphene water is obtained using modified Hummers method Solution, through washing centrifugation repeatedly, ultrasonic 0.5 h, obtains the graphene oxide solution close to neutrality, obtains through lyophilization To the graphene oxide of lamellar, grind and make powder;
(2)Hydrolytic process:Under 40 °C, 1 ml TBT is slowly added in 36.75 ml acetic acid, shape after stirring 24 h Become mixed solution A;
(3)Take 12 mg graphene oxides prepared by step (1) to be added in 20 ml acetic acid, after ultrasonic 0.5 h, obtain oxygen Graphite alkene acetum;
(4)Self assembling process:Under conditions of being stirred continuously, the graphene oxide acetum that step (3) is obtained adds Enter in the mixed solution A being obtained to step (2), stir 2 H-shapeds in 40 °C of lower self assemblies and become mixed solution B;
(5)By step(4)The mixed solution B obtaining transfers to the teflon-lined autoclave of 100 mL In;
(6)Solvent thermal process:Autoclave in step (5) is tightened and puts in baking oven, be incubated 24 h at 150 DEG C; After solvent heat treatment, autoclave is naturally cooled to room temperature, that is, obtain metatitanic acid/graphene oxide pluralgel.
Embodiment 4:
A kind of three-dimensional metatitanic acid/graphene oxide pluralgel, the metatitanic acid/graphene oxide pluralgel of this three dimensional structure Pattern forms fiber cluster by the nanofiber of, two or more than three, and fiber cluster is cross-linked and reticulates structure Gel, the diameter of wherein single nanofiber is about 35 55 nm, and length is about 5 50 μm.As shown in Fig. 2 in Fig. 2 D is the HRTEM figure of the present embodiment pluralgel.In Fig. 3, c is the FESEM figure of the present embodiment pluralgel.In Fig. 4, d is this enforcement The Raman spectrogram of example.
The preparation method of described three-dimensional metatitanic acid/graphene oxide pluralgel is as follows:
(1)With 3 g graphite powders as raw material, jonquilleous acidic oxidation Graphene water is obtained using modified Hummers method Solution, through washing centrifugation repeatedly, ultrasonic 0.5 h, obtains the graphene oxide solution close to neutrality, obtains through lyophilization To the graphene oxide of lamellar, grind and make powder;
(2)Hydrolytic process:Under 40 °C, 1 ml TBT is slowly added in 36.75 ml acetic acid, shape after stirring 24 h Become mixed solution A;
(3)Take 18 mg graphene oxides prepared by step (1) to be added in 20 ml acetic acid, after ultrasonic 0.5 h, obtain oxygen Graphite alkene acetum;
(4)Self assembling process:Under conditions of being stirred continuously, the graphene oxide acetum that step (3) is obtained adds Enter in the mixed solution A being obtained to step (2), stir 2 H-shapeds in 40 °C of lower self assemblies and become mixed solution B;
(5)The mixed solution B that step (4) is obtained transfers to the teflon-lined autoclave of 100 mL In;
(6)Solvent thermal process:Autoclave in step (5) is tightened and puts in baking oven, be incubated 24 h at 150 DEG C; After solvent heat treatment, autoclave is naturally cooled to room temperature, that is, obtain metatitanic acid/graphene oxide pluralgel.
Embodiment 5:
A kind of three-dimensional metatitanic acid/graphene oxide pluralgel, the metatitanic acid/graphene oxide pluralgel of this three dimensional structure Pattern forms fiber cluster by the nanofiber of, two or more than three, and fiber cluster is cross-linked and reticulates structure Gel, the diameter of wherein single nanofiber is about 35 55 nm, and length is about 5 50 μm.As shown in Fig. 2 in Fig. 2 E is the HRTEM figure of the present embodiment pluralgel, and 3f is the HRTEM enlarged drawing of the present embodiment pluralgel.In Fig. 3, d is this enforcement The FESEM figure of example pluralgel.
The preparation method of described three-dimensional metatitanic acid/graphene oxide pluralgel is as follows:
(1)With 3 g graphite powders as raw material, jonquilleous acidic oxidation Graphene water is obtained using modified Hummers method Solution, through washing centrifugation repeatedly, ultrasonic 0.5 h, obtains the graphene oxide solution close to neutrality, obtains through lyophilization To the graphene oxide of lamellar, grind and make powder;
(2)Hydrolytic process:Under 40 °C, 1 ml TBT is slowly added in 36.75 ml acetic acid, shape after stirring 24 h Become mixed solution A;
(3)Take 24 mg graphene oxides prepared by step (1) to be added in 20 ml acetic acid, after ultrasonic 0.5 h, obtain oxygen Graphite alkene acetum;
(4)Self assembling process:Under conditions of being stirred continuously, the graphene oxide acetum that step (3) is obtained adds Enter in the mixed solution A being obtained to step (2), stir 2 H-shapeds in 40 °C of lower self assemblies and become mixed solution B;
(5)The mixed solution B that step (4) is obtained transfers to the teflon-lined autoclave of 100 mL In;
(6)Solvent thermal process:Autoclave in step (5) is tightened and puts in baking oven, be incubated 24 h at 150 DEG C; After solvent heat treatment, autoclave is naturally cooled to room temperature, that is, obtain metatitanic acid/graphene oxide pluralgel.
Embodiment 6:
A kind of three-dimensional metatitanic acid/graphene oxide pluralgel, the metatitanic acid/graphene oxide pluralgel of this three dimensional structure Pattern forms fiber cluster by the nanofiber of, two or more than three, and fiber cluster is cross-linked and reticulates structure Gel, the diameter of wherein single nanofiber is about 35 55 nm, and length is about 5 50 μm.
The preparation method of described three-dimensional metatitanic acid/graphene oxide pluralgel is as follows:
(1)With 2 g graphite powders as raw material, jonquilleous acidic oxidation Graphene water is obtained using modified Hummers method Solution, through washing centrifugation repeatedly, ultrasonic 1 h, obtains the graphene oxide solution close to neutrality, obtains through lyophilization The graphene oxide of lamellar, grinds and makes powder;
(2)Hydrolytic process:Under 30 °C, 0.5 ml TBT is slowly added in 36.75 ml acetic acid, after stirring 12 h Form mixed solution A;
(3)Take 6 mg graphene oxides prepared by step (1) to be added in 5 ml acetic acid, after ultrasonic 1h, obtain graphite oxide Alkene acetum;
(4)Self assembling process:Under conditions of being stirred continuously, the graphene oxide acetum that step (3) is obtained adds Enter in the mixed solution A being obtained to step (2), stir 2 H-shapeds in 30 °C of lower self assemblies and become mixed solution B;
(5)By step(4)The mixed solution B obtaining transfers to the teflon-lined autoclave of 100 mL In;
(6)Solvent thermal process:Autoclave in step (5) is tightened and puts in baking oven, be incubated 24 h at 120 DEG C; After solvent heat treatment, autoclave is naturally cooled to room temperature, that is, obtain metatitanic acid/graphene oxide pluralgel.
Embodiment 7:
A kind of three-dimensional metatitanic acid/graphene oxide pluralgel, the metatitanic acid/graphene oxide pluralgel of this three dimensional structure Pattern forms fiber cluster by the nanofiber of, two or more than three, and fiber cluster is cross-linked and reticulates structure Gel, the diameter of wherein single nanofiber is about 35 55 nm, and length is about 5 50 μm.
The preparation method of described three-dimensional metatitanic acid/graphene oxide pluralgel is as follows:
(1)With 2 g graphite powders as raw material, jonquilleous acidic oxidation Graphene water is obtained using modified Hummers method Solution, through washing centrifugation repeatedly, ultrasonic 0.8 h, obtains the graphene oxide solution close to neutrality, obtains through lyophilization To the graphene oxide of lamellar, grind and make powder;
(2)Hydrolytic process:Under 35 °C, 0.2 ml TBT is slowly added in 36.75 ml acetic acid, shape after stirring 18h Become mixed solution A;
(3)Take 6 mg graphene oxides prepared by step (1) to be added in 5 ml acetic acid, after ultrasonic 1h, obtain graphite oxide Alkene acetum;
(4)Self assembling process:Under conditions of being stirred continuously, the graphene oxide acetum that step (3) is obtained adds Enter in the mixed solution A being obtained to step (2), stir 2 H-shapeds in 35 °C of lower self assemblies and become mixed solution B;
(5)By step(4)The mixed solution B obtaining transfers to the teflon-lined autoclave of 100 mL In;
(6)Solvent thermal process:Autoclave in step (5) is tightened and puts in baking oven, be incubated 12 h at 180 DEG C; After solvent heat treatment, autoclave is naturally cooled to room temperature, that is, obtain metatitanic acid/graphene oxide pluralgel.
Embodiment 8:
A kind of three-dimensional metatitanic acid/graphene oxide pluralgel, the metatitanic acid/graphene oxide pluralgel of this three dimensional structure Pattern forms fiber cluster by the nanofiber of, two or more than three, and fiber cluster is cross-linked and reticulates structure Gel, the diameter of wherein single nanofiber is about 35 55 nm, and length is about 5 50 μm.
The preparation method of described three-dimensional metatitanic acid/graphene oxide pluralgel is as follows:
(1)With 2 g graphite powders as raw material, jonquilleous acidic oxidation Graphene water is obtained using modified Hummers method Solution, through washing centrifugation repeatedly, ultrasonic 0.8 h, obtains the graphene oxide solution close to neutrality, obtains through lyophilization To the graphene oxide of lamellar, grind and make powder;
(2)Hydrolytic process:Under 35 °C, 1ml TBT is slowly added in 36.75 ml acetic acid, is formed after stirring 18 h Mixed solution A;
(3)Take 12 mg graphene oxides prepared by step (1) to be added in 20 ml acetic acid, after ultrasonic 1h, obtain oxidation stone Black alkene acetum;
(4)Self assembling process:Under conditions of being stirred continuously, the graphene oxide acetum that step (3) is obtained adds Enter in the mixed solution A being obtained to step (2), form mixed solution B in 40 °C of lower self assembly stirring 1h;
(5)By step(4)The mixed solution B obtaining transfers to the teflon-lined autoclave of 100 mL In;
(6)Solvent thermal process:Autoclave in step (5) is tightened and puts in baking oven, be incubated 18h at 160 DEG C;Molten After agent heat treatment, autoclave is naturally cooled to room temperature, that is, obtain metatitanic acid/graphene oxide pluralgel.
The present invention adopt simply, a step solvent-thermal method of environmental protection is with positive four butyl esters of graphene oxide and metatitanic acid(TBT)For Raw material, acetic acid is synthesized for solvent.By regulating and controlling the mass ratio of graphene oxide and TBT, to control the formability of gel And stability, by changing the consumption of acetic acid, to control the microscopic appearance of gel.Macroscopic result shows:Non- oxygenation in system During Graphene, define linen solution, not the generation of gel, with the increase of graphene oxide amount(0–24 mg), The formability of gel first improves and is deteriorated until shapeless again;By changing the volume of acetic acid, result shows sample with acetic acid body Long-pending increase (5 40 ml), formability is become better and better.By Raman spectrum, high-resolution-ration transmission electric-lens(HRTEM), Flied emission sweeps Retouch Electronic Speculum(FESEM)Deng means of testing, the metatitanic acid/graphene oxide gel of three dimensional structure is characterized, result shows:Work as vinegar The volume of acid is less than 10 ml, when the quality of graphene oxide is less than 6 mg, is flower ball-shaped structure;When acetic acid volume be more than etc. In 10 ml, when the quality of graphene oxide is more than or equal to 6 mg, metatitanic acid/graphene oxide complex be by one, two or The fiber composition fiber cluster that person is more than three, fiber cluster reconnects webbed structure, and the diameter of wherein single nanofiber is big It is about 35 55 nm, length reaches tens microns.Using three dimensional structure advantage we will preparation metatitanic acid/graphene oxide multiple Close gel application in the research of photocatalysis performance, result shows that the photocatalysis efficiency of metatitanic acid/graphene oxide pluralgel is pure Metatitanic acid(Not plus graphene oxide, other conditions keep constant)2 times(See Fig. 5).When the content of graphene oxide is 12% (Note:In pluralgel, the ratio of the quality of graphene oxide and the final gross mass of the gel of drying obtaining), photocatalysis Effect is best.In addition the photocatalyst that the present invention is obtained is easily recycled, and preparation method is simple and environmentally-friendly, is industrialization Production provides more probabilities.
Although the above-mentioned accompanying drawing that combines is described to the specific embodiment of the present invention, not model is protected to the present invention The restriction enclosed, one of ordinary skill in the art should be understood that on the basis of technical scheme, and those skilled in the art are not Need to pay the various modifications that creative work can make or deformation still within protection scope of the present invention.

Claims (10)

1. a kind of three-dimensional metatitanic acid/graphene oxide pluralgel, is characterized in that:The pattern of this pluralgel is by some nanometers Fiber forms fiber cluster, and fiber cluster is cross-linked and reticulates structure;
This pluralgel is prepared by the following preparation method:
(1) prepare graphene oxide;
(2) hydrolytic process:Positive for metatitanic acid four butyl esters (TBT) are added in acetic acid, after stirring, form mixed solution A;
(3) prepare graphene oxide acetum:Take graphene oxide prepared by step (1) to mix with acetic acid, ultrasonic obtain oxygen Graphite alkene acetum;
(4) self assembling process:The graphene oxide acetum that the prepared mixed solution A of step (2) and step (3) are obtained mixes Even, self assembly stirring at 30~40 DEG C forms mixed solution B;
(5) the mixed solution B that step (4) obtains is incubated 12~24h at 120~180 DEG C, after solvent heat treatment, is cooled to room Temperature, that is, obtain metatitanic acid/graphene oxide pluralgel.
2. gel as claimed in claim 1, is characterized in that:A diameter of 35 55nm of single nanofiber, length is 5 50 μ m.
3. the preparation method of three-dimensional metatitanic acid/graphene oxide pluralgel as claimed in claim 1 or 2, is characterized in that, including Following steps:
(1) prepare graphene oxide;
(2) hydrolytic process:Positive for metatitanic acid four butyl esters (TBT) are added in acetic acid, after stirring, form mixed solution A;
(3) prepare graphene oxide acetum:Take graphene oxide prepared by step (1) to mix with acetic acid, ultrasonic obtain oxygen Graphite alkene acetum;
(4) self assembling process:The graphene oxide acetum that the prepared mixed solution A of step (2) and step (3) are obtained mixes Even, self assembly stirring at 30~40 DEG C forms mixed solution B;
(5) the mixed solution B that step (4) obtains is incubated 12~24h at 120~180 DEG C, after solvent heat treatment, is cooled to room Temperature, that is, obtain metatitanic acid/graphene oxide pluralgel.
4. method as claimed in claim 3, is characterized in that:In step (1), described prepare graphene oxide step be:With Graphite powder is raw material, obtains jonquilleous acidic oxidation graphene aqueous solution using modified Hummers method, through water repeatedly Wash centrifugation, ultrasonic 0.5 1h, obtain graphene oxide solution, graphene oxide solution now close to neutral, through dry To the graphene oxide of lamellar, grind and make powder.
5. method as claimed in claim 3, is characterized in that:In step (2), the reaction temperature of hydrolytic process is 30 40 DEG C, TBT and acetic acid (V1) volume ratio be:(0.1~1):(30~50), mixing time is 12~24h.
6. method as claimed in claim 3, is characterized in that:In step (3), described graphene oxide and acetic acid (V2) quality Volume ratio is:(2~24):(5~40) mg/mL, ultrasonic time is 0~1h.
7. method as claimed in claim 3, is characterized in that:In step (4), the time of self assembly stirring is 1 2h.
8. method as claimed in claim 3, is characterized in that:In step (5), specific operating procedure is:The mixing obtaining is molten Liquid B transfers in teflon-lined autoclave;Autoclave is tightened and puts in baking oven, at 120~180 DEG C Insulation 12~24h;After solvent heat treatment, autoclave is naturally cooled to room temperature, that is, obtain metatitanic acid/graphene oxide and be combined Gel.
9. method as claimed in claim 3, is characterized in that:Described TBT with the volume mass ratio of graphene oxide is:(0.1~ 1):(5~24) mL/mg, acetic acid (V in described step (2)1) with step (3) in acetic acid (V2) volume ratio be:(30~50): (5~40).
10. method as claimed in claim 3, is characterized in that:In step (4), described self assembling process condition is 40 DEG C of guarantors Hold 2h.
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